JPH05302033A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having improved toughness without detriment to the heat resistance, mechanical properties, electrical properties and adhesiveness inherent in the constituent curable resin by combining the curable resin with a curing agent, a polysiloxane compound and a specified block copolymer. CONSTITUTION:The title composition comprises a curable resin, a curing agent, a polysiloxane compound and a block copolymer obtained by the polymerization of an aromatic resin precursor compatible with the curable resin with a polysiloxane intermediate. As the aromatic resin precursor, a polyamide resin, a polyimide resin or a polyamide imide resin is desirable, and such resins each containing phenolic hydroxyl groups in the main chain are particularly desirable. As the curable resin, an epoxy resin is particularly desirable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to modification of a curable resin composition in which a polysiloxane compound is dispersed in a curable resin, and more particularly to a curable resin composition having improved toughness.

[0002]

Curable resins represented by phenolic resins, amino resins, epoxy resins, and urethane resins have excellent heat resistance, mechanical properties, electrical properties, and adhesiveness. Circuit board with these layers
Furthermore, semiconductor chips, coils, sealants for electric circuits, adhesives, paints, fiber-reinforced resins, etc. are used in a very wide range, but curable resins are generally fragile and have insufficient toughness. There are problems such as easy cracking and easy peeling, which are a major obstacle to the expansion of applications while maintaining their excellent properties. For such problems, polyimide, polyamide, polycarbonate, polybutadiene,
Attempts have been made to increase the toughness by adding and dispersing a thermoplastic resin such as polybutadiene acrylonitrile copolymer and polysiloxane, but the sufficient effect has not been obtained yet. Especially in the electric and electronic industries, there is a strong demand for improving toughness,
In order to solve these problems, and in consideration of lowering the dielectric constant, polysiloxane resins have been used. However, the polysiloxane-based resin has a problem that the dispersion stability of the polysiloxane-based resin cannot be sufficiently obtained because of poor compatibility with the curable resin, and stable composite characteristics cannot be obtained. ing.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of these problems, and while maintaining the heat resistance, mechanical characteristics, electrical characteristics and adhesiveness of the curable resin,
It is to provide a curable resin composition having improved toughness.

[0004]

As a result of intensive studies to solve the above problems, the present inventor dispersed a polysiloxane compound in a curable resin, and further prepared a compatibilizing agent for the polysiloxane compound. As a result, they have found that the above problems can be solved by using a block copolymer composed of an aromatic resin and a polysiloxane compound, and completed the present invention. That is, the curable resin composition of the present invention comprises (A) a curable resin and a curing agent, (B) a polysiloxane-based compound, (C) an aromatic resin precursor compatible with the curable resin, and a polysiloxane-based compound. It is characterized by containing a block copolymer obtained by a polymerization reaction of an intermediate.

The curable resin used in the present invention includes formaldehyde condensation type resin, carboxyl group condensation type resin, vinyl polymerization type resin and the like, and specifically, phenol resin, amino resin, urethane resin, epoxy resin and the like. And these may be used alone or in combination. Of these curable resins, epoxy resins are preferably used in the present invention.

The epoxy resin used as the curable resin composition in the present invention may be any polyfunctional resin, for example, glycidyl ethers, glycidyl esters, glycidyl amines, linear aliphatics. Examples of the resin include epoxides, alicyclic epoxides, hydantoin type epoxies, and the like. Examples of glycidyl ethers include glycidyl ether of bisphenol, polyglycidyl ether of phenol novolac, alkylene glycol or glycidyl ether of polyalkylene glycol. The glycidyl ether of bisphenol includes bisphenol A type, bisphenol F type, and bisphenol AD.
Type, bisphenol S type, tetramethylbisphenol A type, tetramethylbisphenol F type, tetramethylbisphenol AD type, tetramethylbisphenol S type
Type, tetrachlorobisphenol A type, tetrabromobisphenol A type and the like diglycidyl ether is a polyglycidyl ether of phenol novolac, for example, novolac resin such as phenol novolac, cresol novolac, brominated phenol novolac. Examples of the polyglycidyl ether of alkylene glycol or diglycidyl ether of polyalkylene glycol include diglycidyl ethers of glycols such as polyethylene glycol, polypropylene glycol and butanediol. The glycidyl esters include, for example, glycidyl ester of hexahydrophthalic acid and glycidyl ester of dimer acid, and the glycidyl amines include, for example, triglycidylaminodiphenylmethane, triglycidylaminophenol, triglycidyl isocyanate. And so on. Furthermore,
Examples of linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil, and examples of alicyclic epoxides include 3,4-epoxy-6-methylcyclohexylmethylcarboxylate,
3,4-epoxy cyclohexyl methyl carboxylate, hydrogenated bisphenol epoxy and the like can be mentioned. Examples of hydantoin-type epoxies include diglycidylhydantoin and glycidylglycidoxyalkylhydantoin. INDUSTRIAL APPLICABILITY The present invention is preferably used as an effective means for an epoxy resin as a curable resin which has a high crosslink density and is brittle.

Specific examples of the phenol resin used as the curable resin in the present invention include phenol, cresol, xylenol, alkylphenols, cyclohexylphenol, phenylphenol, halogen group-containing phenols, bisphenolmethane, bisphenol ether and bisphenolpropane. Examples thereof include phenol resins mainly composed of a condensation product of phenols such as resorcin and formaldehyde, and modified phenol resins thereof. Further, there are novolac type and resol type as the types of these phenol resins, but there is no limitation in the present invention. Specific examples of the amino resin include urea, melamine, benzoguanamine-based compounds such as benzoguanamine and condensation products of amine-based compounds such as aniline and formaldehyde, and further ethylene glycol,
Examples include those obtained by modifying this condensate with alkane polyols such as glycerin, polyalkylene ether polyols, alcohols and the like. Further, the urethane resin includes a polyhydric alcohol, a polyvalent amine compound, a compound having a hydroxyl group or an amino group at the end, a resin obtained by an addition reaction of an acrylic polyol or the like with a polyvalent isocyanate compound, and further, these resins It may be modified with alcohol, phenol, diethylamine, oxime, oil and fat.

The polysiloxane compound used in the present invention is dimethyl silicone oil, olefin modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, fluorine modified silicone oil, amino modified silicone oil, aminoaryl modified silicone oil. , Mercapto-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbana-modified silicone oil, amide-modified silicone oil, higher fatty acid-modified silicone oil, alkoxy-modified silicone oil, polyalkylphenylsiloxane, methylphenylpolysilsesquioxane, cross-linking Specific examples include type silicon and the like. Among these, carboxyl-modified silicone oil, that is, polysiloxane having carboxyl groups at both ends (trade name: XF42
-508, average molecular weight: 2000, manufactured by Toshiba Silicon Co., Ltd., amine-modified silicone oil, that is, polysiloxane having amino groups at both ends (trade name: X-22-16).
1B, average molecular weight 3000, manufactured by Shin-Etsu Chemical Co., Ltd., epoxy-modified silicone oil, that is, polysiloxane having epoxy groups at both ends (trade name: FM5521, average molecular weight 5000, manufactured by Chisso Corporation), and other α, ω-bis (3 −
Mercaptopropyl) polysiloxane (trade name: TSL
9886, average molecular weight: 880, manufactured by Toshiba Silicon Co.) and the like can be preferably used in the present invention.

When the curable resin is an epoxy resin, the curing agent used in the present invention is, for example, triphenylphosphine, bis (4-aminophenyl) sulfone, bis (4-).
Aminophenyl) methane, 1,5-diaminonaphthalene, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,
Aromatic amine compounds such as 4-benzenediamine, 1,3-di (p-aminophenyl) propane, m-xylenediamine, triethanolamine, ethylenediamine,
Diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, mensendiamine, isophoronediamine, bis (4
-Amino-3-methyldicyclohexyl) methane, polymethylenediamine, polyetherdiamine and other aliphatic amine compounds, polyaminoamide compounds, dodecyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, and other aliphatic acids Anhydrides, alicyclic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tris trimellitate Novolak resins such as aromatic acid anhydrides such as phenol, cresol, alkylphenol, catechol, bisphenol A type, bisphenol F type, and halides of these phenol resins, amino resins, urea resins,
Examples thereof include, but are not limited to, melamine resins, dicyandiamide and dihydrazine compounds, imidazole compounds, Lewis acids and Bronsted acid salts, polymercaptan compounds, isocyanates and blocked isocyanate compounds.

Further, when the curable resin in the present invention is a phenol resin and an amino resin, for example, acid catalysts such as P-toluenesulfonic acid, dodecylbenzenesulfonic acid, phosphoric acid and its derivatives, hexamethylenetetramine, tributylamine, Cobalt octanate, lead octanate, and the like, and in the case of urethane resin, a polyvalent amine compound, a polyhydric alcohol, a polyester having a hydroxy group at the terminal and the like can be applied as the curing agent constituting the present invention.

The block copolymer used in the present invention is
Since it is produced by the polymerization reaction of an aromatic resin precursor having a functional group at the terminal and a polysiloxane intermediate,
It is preferable that the intrinsic viscosity in a dimethylacetamide solution at a temperature of 0.5% and a concentration of 0.5% is in the range of 0.1 to 3.0 dl / g. In this case, the block copolymer has an intrinsic viscosity of 0.
If it is less than 1 dl / g, there is no effect of improving the toughness.
If it is greater than 0 dl / g, the viscosity of the curable resin will increase,
It is not preferable in terms of workability. The combination of the functional groups at the time of reacting the aromatic-based resin precursor having a functional group at the terminal with the polysiloxane-based intermediate is an —OH group,
-NH group, -SH group or -COOH group and -NCO group,
Or a combination with a glycidyl group, a combination of a vinyl group with an —NH group or an —SH group, a Si—OH group or a Si
Examples thereof include a combination of an —OCH ₃ group and an —OH group.
In order to obtain such a combination, it is possible to modify the ends of these aromatic resin precursors or polysiloxane intermediates, if necessary.

The aromatic resin precursor constituting the block copolymer used in the present invention is compatible with the curable resin to prevent a decrease in glass transition temperature caused by the introduction of the polysiloxane compound. Examples thereof include polyester resins, polyarylene ether sulfone resins, polyether ketone resins, polysulfone resins, polyetherimide resins, polyamide resins, polyimide resins, polyamideimide resins, polycarbonate resins, polyurethane resins, and the like. Among these, a polyamide resin, a polyimide resin, or a polyamideimide resin having a high heat resistance and a rigid structure can be preferably used in the present invention. Further, these resins can react with the curable resin at a relatively low temperature by containing a phenolic hydroxyl group as a functional group in the main chain, and can obtain more stable composite properties.

The polyamide resin, polyimide resin or polyamideimide resin which is preferably used as the aromatic resin precursor in the present invention is easily synthesized by a polycondensation reaction between a dicarboxylic acid, a tetracarboxylic acid anhydride and a diamine compound. be able to. In this case, a carboxyl group at the terminal, a dicarboxylic acid compound having a functional group such as an amino group or a diamine compound by a polymerization method using an excess of one, the carboxyl group at the terminal of the polyamide resin, polyimide resin or polyamideimide resin Alternatively, an amino group can be introduced.

Further, as a part of the dicarboxylic acid component or the diamine component, for example, phenolic properties such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid and 2-hydroxyterephthalic acid. Dicarboxylic acid having hydroxyl group, or N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide, 3,3'-dihydroxy-
By using a diamine containing a phenolic hydroxyl group such as 4,4'-diaminodiphenylmethane, a phenolic hydroxyl group-containing polyamide resin, polyimide resin or polyamideimide resin can be obtained. Further, the block copolymer used in the present invention can be obtained by polymerizing an aromatic resin precursor having such a terminal functional group and a polysiloxane intermediate having a carboxylic acid group or an amino group at the terminal. it can.

The polymerization reaction for producing such a block copolymer comprising a polyamide resin, a polyamideimide resin or a polyimide resin having a phenolic hydroxyl group and a polysiloxane-based intermediate is carried out, for example, with a phosphite ester. It can be carried out by stirring in an organic solvent represented by N-methyl-2-pyrrolidone in the presence of a pyridine derivative under an inert atmosphere such as nitrogen.
This polymerization reaction is preferable because it can be carried out at a low temperature, side reactions hardly occur, and it can be carried out without protecting the phenolic hydroxyl group contained in these resins.

The blending amount of each of the components (A) to (C) used in the present invention is such that the total amount of the curable resin and the curing agent of (A) is 100 parts, and the polysiloxane type of (B) is used. The amount of the compound is usually preferably in the range of 1 to 30 parts, and if it is too small, the effect of improving the toughness is scarce, and if it is too large, not only the effect of the toughness is reduced but also the viscosity of the curable resin becomes high and the handleability is deteriorated. Absent. Further, in the block copolymer of (C), the polysiloxane part not only promotes the dispersion stabilization of the polysiloxane compound of (B), but the aromatic resin part of the block copolymer has the above-mentioned (A). Since it is molecularly dispersed in the curable resin to improve the toughness of the curable resin, its addition amount is preferably about 1 to 20 parts. If this amount is too small, the effect cannot be produced. Also,
If the amount is too large, the viscosity of the curable resin is remarkably increased and the handleability is deteriorated, which is not preferable.

The curable resin composition in the present invention comprises a curable resin and a block copolymer obtained by a polymerization reaction of an aromatic resin precursor compatible with the curable resin and a polysiloxane intermediate. A reaction mixture is reacted in the presence of a curing catalyst to prepare a resin mixture composed of a curable resin modified product and an unreacted curable resin, and then the mixture is mixed with a polysiloxane compound, and a curing agent is further added, It can be manufactured by stirring and mixing. The mixture in this case can also be performed using a solvent.

The curable resin composition of the present invention can be formed by the above method, but other additives can be added to the composition, if necessary. For example,
Organic solvents such as toluene, ethanol, cellosolve, tetrahydrofuran, dimethylformamide, plasticizers such as natural waxes, synthetic waxes and metal salts of long-chain fatty acids, mold release agents such as acid amides, esters and paraffins , Nitrile rubber, butadiene rubber and other stress relaxation agents, chlorinated paraffin, bromtoluene, hexabromobenzene, antimony trioxide and other flame retardants, silane coupling agents, titanate coupling agents, aluminum coupling agents, etc. Coupling agent, fused silica, crystalline silica, low α-ray silica, glass flakes, glass beads, glass balloons, talc, alumina, calcium silicate, aluminum hydroxide, calcium carbonate,
Barium sulfate, magnesia, silicon nitride, boron nitride,
Ferrite, rare earth cobalt, gold, silver, nickel, copper,
Metal powders such as lead, iron powder, iron oxide, iron sand, graphite, carbon,
Rouge. Inorganic filler such as yellow lead or coloring agent such as dye or pigment such as conductive particles, carbon fiber, glass fiber, boron fiber,
Inorganic fiber such as silicon carbide fiber, alumina fiber, silica-alumina fiber, organic fiber such as aramid fiber, polyester fiber, cellulose fiber, carbon fiber, oxidation stabilizer, light stabilizer, moisture resistance improver, thixotropy imparting agent , Diluents, defoamers, various other resins, tackifiers,
An antistatic agent, a lubricant, an ultraviolet absorber, etc. can also be blended.

To cure the curable resin of the present invention, curing with a catalyst, oxygen or moisture at room temperature, heat curing with or without addition of a curing agent or curing catalyst, or acid generated by ultraviolet irradiation is used. A method such as catalyst curing can be used.

Further, the curable resin composition of the present invention can be used in various shapes such as solid, powder, paste, liquid and sheet, and can have a shape according to the purpose of use. . In addition, as applications of these, coils, capacitors, transistors, ICs, thermistors, resistors, for casting for the insulation of liquid crystal, for molding,
It can be used as a material for potting, sealing, bonding, coating, and the like.

[0021]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 <Polyamide containing phenolic hydroxyl group (about 2 mol%)-
Synthesis of polysiloxane block copolymer> Isophthalic acid 19.60 g (118 mmol), 3,4'-oxydianiline 26.4 g (132 mmol), 5-hydroxyisophthalic acid 0.41 g (2.3 mmol),
Lithium chloride 3.9g, calcium chloride 12.1
g, N-methyl-2-pyrrolidone (240 ml) and pyridine (54 ml) were placed in a 1-liter 4-neck round bottom flask, and the mixture was stirred and dissolved, and then triphenyl phosphite 74 was added.
g was added and reacted at 90 ° C. for 4 hours to produce a phenolic hydroxyl group-containing polyamide oligomer having aminoaryl groups at both ends. Next, a polysiloxane having carboxyl groups at both ends is added to the polyamide oligomer (trade name: XF42-508, average molecular weight: 2000,
2) 46.2 g (about 14 mmol) manufactured by Toshiba Silicon Co., Ltd.
After adding a liquid dissolved in 40 ml of pyridine and reacting for another 4 hours, the reaction liquid was cooled to room temperature, and then the reaction liquid was added to 20 liters of methanol so that the content of the polysiloxane part used in the present invention was about 50 wt. %, A polyamide-polysiloxane block copolymer containing about 2 mol% of phenolic hydroxyl groups was deposited. The deposited block copolymer was washed with methanol and further refluxed with methanol for purification. The intrinsic viscosity of the block copolymer is 0.
It was 23 dl / g (dimethylacetamide, 30 ° C.). It was measured infrared spectrum by diffusion reflection method a powder of the block copolymer, amide carbonyl group 1674Cm ^-1, the absorption corresponding to -O- group 1183cm ^-1, Si-CH ₃ in 1260 cm ^-1 1090 and 1020
An absorption corresponding to Si-O-Si was observed at cm- ¹ .

Synthesis Example 2 <Preparation of polyamideimide-polysiloxane block copolymer containing phenolic hydroxyl group> Isophthalic acid 14.
2 g (86 mmol), 3,4'-oxydianiline 3
0.0 g (150 mmol), 5-hydroxyisophthalic acid 2.5 g (14 mmol), lithium chloride 3.
9 g, calcium chloride 12.1 g, N-methyl-2-
Pyrrolidone (240 ml) and pyridine (54 ml) were placed in a 1-liter 4-neck round bottom flask, and the mixture was stirred and dissolved. Then, 74 g of triphenyl phosphite was added, and the mixture was heated to 90 ° C.
At room temperature for 4 hours to produce a phenolic hydroxyl group-containing polyamide oligomer having aminoaryl groups at both ends. Then, the polyamide oligomer was added dropwise to methanol to precipitate a polymer, and then methanol washing was repeated to purify. After drying, the purified polymer 13.
3 g, 16 g (50 mmol) of 3,4,3 ', 4'-benzophenone tetracarboxylic acid dianhydride was dissolved in N-methyl-2-pyrrolidone, and reacted at 40 ° C for about 6 hours under a nitrogen atmosphere. Next, a polysiloxane having amino groups at both ends (trade name: X-22-161) is added to the reaction solution.
B, average molecular weight: 3000, manufactured by Shin-Etsu Chemical Co., Ltd.) 30 g was added, and the mixture was further reacted for 8 hours to obtain an amic acid solution. This amic acid solution was heated at 200 ° C. for 2 hours to carry out a dehydration cyclization reaction. After allowing to cool, the polymer solution was poured into a large amount of methanol, the precipitated polymer was filtered off, the filtered product was washed and dried to obtain a phenolic hydroxyl group-containing polyamideimide-polysiloxane block copolymer used in the present invention. A polymer was obtained. The intrinsic viscosity of this block copolymer is 0.32 dl
/ G (dimethylacetamide, 30 ° C). Also was measured infrared spectrum by diffusion reflection method a powder of the block copolymer, amide carbonyl group 1675 cm ^-1, the absorption corresponding to imide groups in 1774 and 1722 cm ^-1, to 1185cm ^-1 -O- The absorption corresponding to the base,
Si-CH ₃ in 1262cm ^-1, 1091 and 1019 cm ^-1
The absorption corresponding to Si-O-Si was observed.

Synthesis example 3 <Preparation of polyimide-polysiloxane block copolymer containing phenolic hydroxyl group> N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide 0.28
g (0.78 mmol) and m-phenylenediamine
4.23 g (39.2 mmol) and 3,4,3 ', 4'
-Benzophenone tetracarboxylic acid dianhydride 16g
(50 mmol) as N-methyl-2-pyrrolidone 45
It was dissolved in 0 mg and reacted at room temperature for 6 hours under a nitrogen atmosphere to obtain a polyamic acid. In this polyamic acid solution, polysiloxanes whose both ends are amino groups (trade name: X
-22-161B, average molecular weight: 3000, manufactured by Shin-Etsu Chemical Co., Ltd.) 30 g (10 mmol) was added, and further 8 at room temperature.
Reacted for hours. This polyamic acid solution was heated at 200 ° C. for 2 hours to carry out a dehydration cyclization reaction. After allowing to cool, the polymer solution was poured into a large amount of methanol, the precipitated polymer was separated by filtration, and the filtered product was washed and dried to obtain a phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer used in the present invention. Got united. The block copolymer has an intrinsic viscosity of 0.33 dl / g (dimethylacetamide, 30
℃). The infrared spectrum of the powder of this block copolymer was measured by the diffuse reflection method.
The absorption corresponding to the imide group at 5 and 1726 cm ^-1 ,
Si-CH ₃ in 1260 cm ^-1, 1090 and of 1020 cm ^-1
The absorption corresponding to Si-O-Si was observed.

Synthesis Example 4 <Preparation of Polycarbonate-Polysiloxane Block Copolymer>2,2'-bis (4-
Hydroxybenzene) propane 20 g (88 mmol)
After dissolving, put in a 500 ml three-necked flask,
Cooled to 10 ° C. Then, carbonyl chloride gas was introduced with stirring to carry out the reaction for about 3 hours. The reaction solution was poured into a large amount of methanol to precipitate a polymer.
The polymer was repeatedly washed with methanol several times and then vacuum dried to obtain 40 g of polycarbonate. Next, this polycarbonate is dissolved in a pyridine solution at 130 ° C.
After heating, 40 g of polysiloxane having epoxy groups at both ends (trade name: FM5521, average molecular weight: 5000, manufactured by Chisso Corporation) was added and reacted for about 4 hours. After the reaction was completed, the reaction solution was added dropwise to a large amount of methanol to precipitate a polymer, which was repeatedly washed and then dried to obtain a polycarbonate-polysiloxane block copolymer. The intrinsic viscosity of this block copolymer was 0.34 dl / g (dimethylacetamide, 30 ° C.). Also was measured infrared spectrum by diffusion reflection method a powder of the block copolymer, the absorption corresponding to -O- group 1185Cm ^-1 is the 1262cm ^-1 Si-CH _3, 1091 and 101
An absorption corresponding to Si-O-Si was observed at 9 cm- ¹ .

Example 1 After dissolving 5 g of the phenolic hydroxyl group-containing polyamide-polysiloxane block copolymer obtained in Synthesis Example 1 in 200 g of tetrahydrofuran, an epoxy resin (Epikote 828, bisphenol A type epoxy resin) was dissolved. , Average molecular weight: 380, epoxy equivalent: 190 ± 5,
95 g of Yuka Shell Co., Ltd. and 0.08 g of triphenylphosphine, which is a curing agent, were added and reacted at 130 ° C. for 2 hours. After completion of the reaction, the reaction solution was vacuum dried at 90 ° C. to obtain a modified epoxy resin in which the phenolic hydroxyl group of the polyamide portion of the phenolic hydroxyl group-containing polyamide-polysiloxane block copolymer was reacted with the epoxide group of the epoxy resin. An epoxy resin mixture consisting of unreacted epoxy resin was obtained. The epoxy resin mixture 1
To a solution of mg in about 30 ml of pyridine, a color indicator of phenolic hydroxyl group (1 g of anhydrous iron (III) chloride is dissolved in 100 ml of chloroform, and then pyridine 8 m
(1) was added, and then the precipitate was filtered to obtain a red solution, and a few drops of the solution were added and stirred. No discoloration was observed, and the epoxy resin mixture contained all glycidyl phenolic hydroxyl groups. After reacting with the group, it was confirmed that no unreacted phenol residue was contained. 80 g of the epoxy resin mixture and 20 g of α, ω-bis (10-carboxyldecyl) polysiloxane having a carboxyl group at both ends (manufactured by Toshiba Silicon Co., average molecular weight about 3300) were added, and after stirring and mixing at 130 ° C., Bis (4-
10 g of aminophenyl) methane and 1 g of triethanolamine, which is a curing catalyst, were added, and the mixture was stirred and uniformly mixed to obtain a curable resin composition of the present invention.

Example 2 5 g of polyamideimide-polysiloxane block copolymer containing phenolic hydroxyl group obtained in Synthesis Example 2, epoxy resin (Epikote 828, bisphenol A type epoxy resin, average molecular weight: 380, epoxy equivalent: 190)
(± 5, manufactured by Yuka Shell Co., Ltd.) 95 g, 0.64 g of triphenylphosphine as a curing agent are dissolved in 200 g of dimethylformamide, and the same operation as in Example 1 is carried out to carry out a phenolic hydroxyl group-containing polyamideimide-polysiloxane. An epoxy resin mixture composed of an epoxy resin modified product obtained by reacting the phenolic hydroxyl group of the polyamideimide portion of the block copolymer with the epoxide group of the epoxy resin and an unreacted epoxy resin was obtained. A solution of 1 mg of the epoxy resin mixture in about 30 ml of pyridine was added to a phenolic hydroxyl group color indicator (anhydrous iron chloride (II
I) 1 g was dissolved in 100 ml of chloroform, 8 ml of pyridine was further added, and then the precipitate was filtered to obtain a red solution, and several drops were added and stirred, but no discoloration was observed. It was confirmed that all of the phenolic hydroxyl groups reacted with the glycidyl group in the epoxy resin mixture, and no unreacted phenol residue was contained. 20 g of the polysiloxane compound used in Example 1 was stirred and uniformly mixed with 80 g of the epoxy resin mixture, and further, at 130 ° C., 12.4 g of bis (4-aminophenyl) methane as a curing agent and tris as a catalyst. Ethanolamine
The curable resin composition of the present invention was obtained by melting and adding 1 g, stirring and mixing uniformly.

Example 3 5 g of the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer obtained in Synthesis Example 3 was dissolved in 200 g of dimethylformamide, and then an epoxy resin (Epikote 828, bisphenol A type epoxy resin, Average molecular weight: 380, epoxy equivalent: 190 ±
5, manufactured by Yuka Shell Co., Ltd.), and 0.08 g of triphenylphosphine as a curing agent were added, and the mixture was reacted at 90 ° C. for 2 hours. After completion of the reaction, the reaction solution was added to water to precipitate a polymer, and washing with warm water was repeated. Tetrahydrofuran was further added to azeotrope these solvents under reduced pressure, followed by vacuum drying, and phenol. An epoxy resin mixture composed of an unmodified epoxy resin and a modified epoxy resin obtained by reacting the phenolic hydroxyl group of the polyimide part of the reactive hydroxyl group-containing polyimide-polysiloxane block copolymer with the epoxide group of the epoxy resin was obtained. To a solution prepared by dissolving 1 mg of this epoxy resin mixture in about 30 ml of pyridine, a phenolic hydroxyl group coloration indicator solution (1 g of anhydrous iron (III) chloride was dissolved in 100 ml of chloroform, and 8 ml of pyridine was added, and the precipitate was filtered. Then, a few drops of a red solution were prepared and stirred, and no discoloration was observed, and all the phenolic hydroxyl groups in the epoxy resin mixture reacted with the glycidyl groups, leaving unreacted phenol residue. It was confirmed that the group was not contained. 80 g of this epoxy resin mixture and 20 g of the polysiloxane compound were uniformly mixed at 130 ° C., and then 12.4 g of bis (4-aminophenyl) methane, which is a curing agent,
1 g of triethanolamine as a catalyst was added, and the mixture was stirred and uniformly mixed to obtain a curable resin composition of the present invention.

Example 4 5 g of the polycarbonate-polysiloxane block copolymer obtained in Synthesis Example 4 and an epoxy resin (Epikote 8
28, bisphenol A type epoxy resin, average molecular weight:
380, epoxy equivalent: 190 ± 5, made by Yuka Shell Co., Ltd.)
95 g, curing catalyst triphenylphosphine
0.64 g was dissolved in 200 g of dimethylformamide, and the same operation as in Example 1 was performed to obtain an epoxy resin mixture containing a polycarbonate-polysiloxane block copolymer. This epoxy resin mixture 80
g, 20 g of the polysiloxane compound and uniformly mixed, and then 12.4 g of bis (4-aminophenyl) methane that is a curing agent and 1 g of triethanolamine that is a catalyst are melted and added, and the mixture is stirred to be uniform. To obtain a curable resin composition of the present invention.

Comparative Example 1 Epoxy resin (Epikote 828, bisphenol A type epoxy resin, average molecular weight: 380, epoxy equivalent: 1
90 ± 5, manufactured by Yuka Shell Co., Ltd.) 100 g of the polysiloxane compound 20 g is uniformly mixed with a solution of bis (4-aminophenyl) methane 12.4 as a curing agent.
g, and 1 g of triphenylphosphine as a curing catalyst
Was added and stirred to obtain a uniform curable resin composition for comparison.

C-shaped washers were put in the resin compositions prepared in Examples 1 to 4 and Comparative Example 1 and heat-cured at 80 ° C. for 2 hours and then at 180 ° C. for 6 hours to prepare test pieces. The cracking temperature of the molded body in which the C-shaped washer was embedded was measured. The measured results are shown in Table-1. The crack generation temperature was measured by the following method. <Measurement Method of Crack Generation Temperature> A test piece in which a C-shaped washer is embedded and a thermistor are integrated, the temperature is gradually lowered with liquid nitrogen, and the temperature at which a crack is generated is read. As is clear from Table 1, it was confirmed that the curable resin composition according to the present invention had a remarkably low crack generation temperature and a remarkable improvement in toughness.

[0031]

[Table 1]

[0032]

The curable resin composition of the present invention has heat resistance,
Since the toughness is remarkably improved without impairing the mechanical properties and the electrical properties, it is useful as a material for electrical and electronic applications in a wide range of fields.

Claims (4)

[Claims] 1. (A) Curable resin and curing agent, (B)
A curable resin containing a polysiloxane compound, (C) a block copolymer obtained by a polymerization reaction of an aromatic resin precursor compatible with the curable resin and a polysiloxane intermediate. Composition. 2. The curable resin composition according to claim 1, wherein the curable resin is an epoxy resin. 3. The curable resin composition according to claim 1, wherein the aromatic resin precursor is a polyamide resin, a polyimide resin or a polyamideimide resin. 4. The curable resin composition according to claim 3, wherein the polyamide resin, the polyimide resin, or the polyamide-imide resin contains a phenolic hydroxyl group in the main chain.